Additives for lubricants and motor fuels

ABSTRACT

Improved additives for lubricants and motor fuels are provided by a process comprising reacting a petroleum sulfonic acid with an adduct formed from an amine and either urea or thiourea. Lubricating oil compositions and motor fuels containing said additives are also provided.

United States Patent Schiff Sept. 30, 1975 [54] ADDITIVES FOR LUBRICANTSAND 3.068.083 12/1962 Gee et al. 44/73 MOTOR FUELS 3,401,117 9/1968Schiff 252/33 3,438,898 4/1969 Schlobohm et al. 252/33 [75] Inventor:Sidney Schiff, Bartlesville, Okla.

[73} Assignce: g i gi i Company Primary Examiner-Daniel E. Wyman mAssistant E.\'aminer-Mrs. Y. H. Smith [22] Filed: Sept. 6, 1974 Appl.No.: 503,800

US. Cl. 252/33; 44/73; 44/76 Int. Cl Cl0m 1/40 Field of Search 252/33;44/73, 76;

References Cited UNITED STATES PATENTS lO/1955 Palmer, Jr 252/33 9Claims, N0 Drawings ADDITIVES FOR LUBRICANTS AND MOTOR FUELS Thisinvention relates to improvedadditives for lubricants and motor fuels.In one aspect, this invention relates to the preparation of novelcompositions of matter formed from petroleum sulfonic acids and anadduct formed from an amine and either urea or thiourea. In accordancewith another aspect, this invention relates to lubricant compositionscontaining as an additive the reaction product formed from a petroleum.sulfonic acid and an adduct from an amine and either urea or thiourea.In another aspect, this invention relates to motor fuel compositionscontaining as an additive the reaction product formed by contacting apetroleum sulfonic acid with an adduct of an amine and either urea orthiourea.

At the present time it is common practice to enhance or modify certainof the properties of lubricating oils through the use of variousadditives or improvement agents. The lubricating oils employed ininternal combustion engines, such as automotive, light aircraft, anddiesel engines, in particular, require the use of additive agents torender them serviceable under the adverse environmental conditionsfrequently encountered in the operation of these engines. Among thevarious additives employed in modern engine oils, one of the mostimportant is the type which acts to prevent accumulation of sludge inthe crankcase and on the cylinder walls, thereby preventing sticking ofthe piston rings, and the formation of varnish-like coating on thepistons and cylinder walls. Because of their general function ofmaintaining a clean engine, additives of this nature are termeddetergents although it is now understood that they have little utilityin cleaning a dirty engine but by virtue of dispersant activity preventor greatly retard engine fouling.

As cleanliness requirements have called for greater concentrations ofdetergent additives, the problem of ash deposition in the combustionchamber has become more serious. Especially is this a problem in certainengines which tend to develop violent preignition troubles in thepresence if metal-containing ash. These problems have increased theimportance and desirability of using ashless detergents.

An ashless detergent is one which shows substantially no ash when testedby ASTM procedure D-482- 59T. The only possible source of metal whenusing such an additive is that of corrosion products and tracequantities present in some crude oils. It can be generally stated thatmetal-containing deposits in an engine (I) contribute to valve burning,(2) contribute to preignition, (3) tend to foul and short-out sparkplugs, and (4) tend to increase octane requirements. Use of conventionalmetal-containing detergents can contribute to the deposit ofmetal-containing materials in the combustion chamber. Metal-containingdeposits do not form from ashless detergents. Use of an ashlessdetergent, therefore, materially reduces the problems normallyencountered in internal combustion engines in connection withmetal-containing deposits.

It has been found that reaction products having improved detergent anddispersan t properties can be prepared by reacting a petroleum sulfonicacid with an adduct formed from at least one'amine and either urea orthiourea. Thus, broadly speaking, the present invention resides in thereaction product or products obtained when a petroleum sulfonic acid isreacted with an adduct formed from at least one amine and either urea orthiourea as new additives for lubricants and motor fuels; methods ofpreparing said new additives; and lubricant and'motor fuel compositionscontaining said new additives.

An object of this invention is to provide an ashless additive forlubricants.

Another object of this invention is to provide improved additivesexhibiting reduced deposit-forming tendencies in motor fuels.

Another object of this invention is to provide a method for thepreparation of additives for lubricating oils and motor fuels.

Another object of this invention is to provide an improved lubricatingcomposition utilizing the additives of the invention.

Another object of this invention is to provide improved motor fuelcompositions utilizing the additives of the invention.

Other aspects, objects, and advantages of the invention will be apparentto those skilled in the art upon studying this disclosure.

Thus, according to the invention, there is provided new compositions ofmatter comprising the oil-soluble reaction product or products obtainedupon reacting a petroleum sulfonic acid with an adduct formed from atleast one amine and either urea or thiourea.

Further according to the invention, there is provided a process forproducing an additive for lubricants and motor fuels which processcomprises forming an adduct from at least one amine and either urea orthiourea, and then reacting the adduct thus formed with a petroleumsulfonic acid to form said additive.

Further according to the invention, there is provided as a new additivefor lubricants and motor fuels a product additive obtained by theprocess described in the preceding paragraph.

Still further, according to the invention, there is provided newlubricating oil compositions comprising a major proportion of alubricating oil base stock and a minor proportion of a new additive inaccordance with the invention.

Still further, according to the invention, there is provided a new motorfuel composition comprising a major proportion of a motor fuel and aminor proportion of a new additive in accordance with the invention.

A wide variety'of reaction conditions can be employed in the practice ofthe invention. Any reaction conditions under which the reactionsinvolved in the invention will take place are within the scope of theinvention. Similarly, any proportions of reactants which will react witheach other to produce a product additive to the invention are within thescope of the invention. However, as will be understood by those skilledin the art in view of this disclosure, certain reaction conditions andreactant proportions are favored for economic reasons, i.e., thereactions proceed faster and give greater yields for some reactionconditions and some proportions of reactants. The reaction or reactionsinvolved in preparing the product additives of the invention can becarried out in the presence or absence of a diluent which is chemicallyinert, i.e., does not react with'the reactants or reaction products.

Generally speaking, in the practice of the invention the petroleumsulfonic acid and amine/urea or thiourea adduct are preferably reactedin amounts ranging from 1/1 to 3/1 equivalents of petroleum sulfonicacid/mole of amine used to prepare the adduct. A preferred range is 1/1to 2.5/1. Generally speaking, sufficient petroleum sulfonic acid is usedwith the amine adduct to obtain a hydrocarbon-soluble reaction product.However, it is within the scope of the invention to employ operableratios of sulfonic acid to adduct outside said ranges.

The reaction of said adduct and said petroleum sulfonic acid can becarried out at any temperature at which the reaction(s) involved willproceed. Generally speaking, said reaction is preferably carried out attemperatures within the range of about 100 to about 200F. However, it ispresently preferred to employ temperatures in the range of 140 to 150Falthough it is within the scope of the invention to employ operabletemperatures outside said ranges.

A wide range of reaction times can be employed in the practice of theinvention. Generally speaking, the reaction times employed for thereaction of said reactants will be within the range of from about 0.1 toabout 20 hours. However, it is within the scope of the invention toemploy operable times outside said ranges. The reaction can be conductedat any pressure, such as atmospheric pressure, suitable for carrying outthe reactions involved.

It is currently preferred to contact the reactants in the presence of aninert diluent, the most preferred of which is a SAE largely paraffiniclubricating oil base stock in amounts ranging from 02/]. to lO/l partsby weight diluent per part by weight petroleum sulfonic acid. It islikewise currently preferred to add a solution of petroleum sulfonicacid in SAE 10 stock oil (approximately 60 weight percent petroleumsulfonic acid) slowly to a rapidly stirred dispersion of amine/urea orthiourea adduct in SAE 10 stock oil (approximately 30 weight percentadduct) while maintaining the temperature of the reaction system at 140to 150F.

if the currently preferred reaction conditions are employed, no furtherisolation or purification steps are necessary in order to use theproduct in gasoline or lubricating oil formulations. It is currentlypreferred to employ the crude reaction mixture for such purposes asdescribed above without subsequent treatment. In some cases, however, itmay be desirable to isolate and purify the product. Such may beaccomplished by any methods currently known in the art, such asfractional crystallization, solvent extraction, etc.

Generally speaking, any petroleum sulfonic acid prepared in accordancewith methods known in the art can be used as a starting reagent in thepractice of the invention. Methods disclosed in U.S. Pat. No. 3,135,693,issued June 2, 1964, to W. B. Whitney et al., are exemplary of methodswhich can be used in preparing sulfonic acids which can be used in thepractice of this invention.

A wide variety of oils can be used as the charge oil in preparing thepetroleum sulfonic acids used in the practice of the invention.preferably, said charge oil is selected from more viscous bright stockfractions of petroleum. A petroleum fraction having a viscosity of atleast 90 SUS at 210F will produce a petroleum sulfonic acid which issatisfactory in many instances. The deasphalted and solvent refinedpetroleum fractions having a viscosity of about 140 to about 270 SUS at210F are preferred. A presently more preferred sulfonation charge stockis a propane fractionated, solvent extracted, and dewaxed Mid-Continentoil of about 200 to about 230 SUS at 210F. It is preferred that thesulfonation charge stock have a viscosity index of about to 100, or evenhigher.

A Mid-Continent oil is more precisely defined as a mixed base orintermediate base oil in GThe Science of Petroleum, Volume 1, page 7,Oxford University Press, London, New York and Toronto, 1938. The base ofa crude petroleum is defined therein as follows: The base of a crudepetroleum is descriptive of the chemical nature of its mainconstituents. A petroleum may be described as paraffin base, asphaltbase, or mixed base (intermediate base), according to paraffin wax,asphalt, or both paraffin wax and asphalt are present in the residueafter distillation of the lighter components. Typical representatives ofthese three classes are Pennsylvania, Mexican, and Mid-Continentpetroleums, respectively.

The residual material discarded from the propane fractionation stepcontains the rejected asphalt and more aromatic oils. The lube oilfraction, recovered in a propane fractionation step after removal of theSAE 50 lube stock, is extracted with a selective solvent which willseparate the paraffinic hydrocarbons from the more aromatic-typehydrocarbons for removal of these more aromatic-type hydrocarbons toprepare the preferred feedstock. The raffinate from the solventextraction step is then dewaxed.

Sulfonating agents which are known to the art can be utilized in thesulfonation step in preparing said petroleum sulfonic acids. Sulfonatingagents which can be so used including fuming sulfuric acid and liquid S0Said fuming sulfuric acid can vary from 10 weight percent to 40 weightpercent excess S0 However, when sulfuric acid is used it is usuallypreferred to use commercial fuming sulfuric acid which contains about 20weight percent excess S0 Liquid S0 i.e., liquid 50:, in liquid S0 is thepresently preferred sulfonating agent for use in the practice of theinvention. Such liquid 80;, is commercially available.

When 20 percent fuming sulfuric acid is used as the sulfonating agent,the acid-oil ratio can be in the range of from about 0.1:1 to about0.7:1, or even 1:1 to produce the petroleum sulfonic acids used in thepractice of the invention. A preferred range of acid-oil ratios is inthe range of about 0.3 to about 0.6:1. When liquid S0 in liquid S0 isthe sulfonation agent, the 50;, to oil weight ratios are maintainedequivalent to those available from the 20 percent fuming sulfuric acidvalues given above. In other words, the S0 to oil ratio can be in therange of about 0.02 to 0.2, preferably about 0.06 to about 0.12:1. SaidS0 to oil ratios can be controlled by varying the rate of flow of theoil or of the S0 containing medium, or both. The above given ratios areweight ratios.

Sulfonation temperatures can be controlled within the range of about 50to about 200F with the preferred operating range being between about 80and about 150F. At temperatures above about 200F, excessive oxidationwith liberation of sulfur dioxide may take place. A reaction time ofabout 20 to about minutes is preferred when fuming sulfuric acid isutilized as the sulfonating agent in order to provide optimum yield andquality of products. When sulfur trioxide, e.g., sulfur trioxide insulfur dioxide, is utilized as the sulfonation agent, the reaction rateis greatly accelerated and the reaction has been found to besubstantially completed in the time required to accomplish suitablecontact of the oil with the sulfur trioxide, usually less than aboutfive minutes.

The sulfonation reaction can be carried out at atmo spheric pressurealthough pressures greater or less than atmospheric also can beemployed, if desired. When using liquid S0,, in liquid S0 as thesulfonating agent, it is preferred to carry out the reaction atsufficient pressure to maintain the S0 in liquid phase.

As indicated hereinbefore, the above-described petroleum sulfonic acidsare reacted with an adduct formed from at least one amine and eitherurea or thiourea to produce the product additives of the invention.

A wide variety of amines can be used in the practice of the invention.Presently preferred amines for use in the practice of the inventioninclude (a) those containing from 2 to 12 carbon atoms per molecule andrepresented by the formula RNH wherein R is alkyl, cycloaklyl, aryl,alkaryl, aralkyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkylaryl, orarylcycloalkyl and (b) those polyamines represented by the formula HN[(CH ),NH],H wherein x is a whole integer of from 2 to 6, inclusive,and y is a whole integer of from 1 to 10, inclusive. Examples ofsuitable amines which can be used in the practice of the inventioninclude, among others, the following: ethylamine, butylamine,3-methylcyclopentylamine, decylamine, dodecylamine, cyclohexylamine,aniline, naphthylamine, 3,5-diethylcyclohexylamine, m-toluidine,2,3-xylidine, benzylamine, 3-cyclohexylbutylamine, p-cyclohexylaniline,4-phenylcyclohexylamine, 3-methyl-4-phenylcyclopentylamine,ethylenediamine, and its homologs, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, dipropylenetriamine,butylenediamine, hexamethylenediamine, tetrahexenepentamine,heptabutyleneoctamine, decapenteneundecamine, and the like.

The adduct of the above-described amine with either urea or thiourea isprepared by contacting the amine and either urea or thiourea in anamine:urea molar ratio of 1:1 to 2.5:1 with 1.5:1 to 2.25:1 currentlybeing preferred. Said contacting is done under any conditions of time,temperature, and pressure which result in the desired product.Ordinarily, the reaction temperatures will be in the range of about 100to about 350F. Reaction times will be about 0.5 to about hours. Anyconvenient pressure, such as atmospheric, can be used. It is currentlypreferred to heat the reaction mixture slowly to about 300F to controlammonia evolution and reduce foaming, thereafter maintaining thetemperature at about 300F until ammonia evolution subsides or about fourhours. If desired, an inert gas such as nitrogen can be bubbled throughthe reaction mixture.

It is sometimes desirable to pressurize the reactor with an inert gas tomaintain the adduct forming reactants predominantly in the liquid phase,for example, from 0 to about 2,000 psig.

On occasion, it is desirable to employ an inert diluent in theproduction of the adduct of the amine and urea or thiourea. Suchdiluents include saturated aliphatic and cycloaliphatic hydrocarbons,aromatic hydrocarbons, etc. The presently preferred mode of operation isin the absence of diluent.

The adduct of the amine and either urea or thiourea can be isolated andpurified by any convenient means, such as fractional distillation,crystallization, solvent extraction, etc. However, it is currentlypreferred to employ the crude reaction mixture for contacting with thepetroleum sulfonic acid to produce the inventive composition.

The compositions of this invention, when used as a gasoline additive,are added directly to gasoline in either a purified state or as a crudereaction mixture as hereinbefore described. The quantity of additiveutilized is in the range of 0.001 to 0.2, preferably 0.01 to 0.1, partsby weight additive per 100 parts by weight gasoline. When gasolinecontaining this additive is utilized in conventional internal combustionengines, the buildup of hard refractory deposits on intake valves issubstantially diminished. In addition, the additive in gasoline iseffective as an upper cylinder lubricant, a carburetor cleaner, asolvent for valve deposits, and a fuel line cleaner.

The gasolines into which the invention additives are dispersed areconventional motor fuel distillates boiling in the range of 420F.Gasolines or automotive fuels to which the described additives performthe functions described include substantially all grades of gasolinepresently being employed in automotive and internal combustion aircraftengines. Generally, automotive and aircraft gasolines contain bothstraight-run and cracked stock with or without alkylated hydrocarbons,reformed hydrocarbons, and the like. Such gasolines can be prepared fromsaturated hydrocarbons, e.g., straight-run stocks, alkylation products,and the like, with or without gum inhibitors and with or without solublelead compounds as, for example, tetraethyl lead (T.E.L) or ethyl fluid.The gasolines may contain as much as about 5 ml of T.E.L. per gallon,such amounts being used commercially in aviation gasolines. These can beleaded or non-leaded and can contain other conventional fuel additivessuch as antioxidants and the like.

The compositions of this invention are oil-soluble and can beincorporated in lubricating oil formulations in combinations dependingon specific service requirements. For example, in many general dutycrankcase oil applications, the additives of the invention can beblended with appropriate base oils and other additives to provide highquality lubricating oils which meet the requirements and specificationsfor their intended use.

Generally speaking, the compositions of this invention can be added tothe base lubricating oil in any amount sufficient to produce the desireddegree of improvement. For example, the additives can be used in amountsranging from 0.2 to 30 weight percent of the finished oil. A presentlypreferred concentration of petroleum sulfonic acid addition product isin the range of about 1 to 12 weight percent of finished oil.

The lubricating oils to which the invention compositions can be addedinclude any suitable mineral oils of lubricating viscosity, such asthose used for compounding lubricating oils of SAE 10 to SAE 50viscosity.

These oils can be derived from suitable naphthenic, paraffinic, andmixed base crudes. The lube oils can also contain other additives suchas thickeners and the like.

EXAMPLE I A petroleum sulfonic acid was prepared in Run 1 from asolvent-refined, dewaxed lubricating oil fraction derived fromMid-Continent petroleum and having the following properties: viscosityof about 4200 SUS at F and about 210 SUS at 210F and viscosity index ofabout 97. This oil was sulfonated with a 10 percent SO -90 percent Smixture in a continuous operation substantially like that described byWhitney et al., US. Pat. No. 3,135,693. The SO /Oil weight ratio wasabout 0.08 and the temperature of the reaction was controlled at about 115F. The total reaction time, including mixing and soaking periods, wasabout five minutes. The system was maintained in liquid phase at apressure of 100-120 psig. Effluent from the sulfonation unit wassubjected to a two-stage flash for SO -S0 removal.

EXAMPLES II to VII The following runs illustrate the preparation ofadducts of tetraethylenepentamine (TEPA) and urea or thiourea.

In Run 2 TEPA (108 gm) was placed in a 250 ml reactor and heated to115F. Urea (16 gm) was added slowly over a 10-minute period. The mixturewas heated rapidly with stirring to 285F and then slowly (1.5 hours) to295F. The system was maintained at 295 to 305F for 3.5 hours withnitrogen bubbling through it. Elemental analyses of the crude reactionmixture are recorded in Table 1.

Run 3 involved the same reactants and similar conditions as Run 2.Following mixture of the reactants the temperature was increased from220F to 300F in two hours and was maintained at 300F for 10 hours withnitrogen bubbling through it. Elemental analyses of the crude reactionmixture are given in Table I.

In Runs 4 and 5 TEPA (1 19.7 gm) was heated with stirring to 125F in a250 ml reactor. Thiourea (22.8 gm) was added slowly over a 5-minuteperiod. After the mixture was heated rapidly to 240F and then slowly(1.5 hours) to 300F, the temperature was maintained at 300 to 315F forfour hours during which a stream of nitrogen was bubbled through thereaction mixture. Elemental analyses of the crude reaction mixtures aregiven in Table I. Runs 6 and 7 were conducted using the same reactantsand similar conditions to those de scribed for Runs 4 and 5. The onlydifferences employed in Run 6 were the use of 180 gm TEPA and 34.3 gmthiourea and maintenance of the temperature at 300F for two hours withnitrogen bubbling through the system. Elemental analyses are included inTable I.

"Calculated for [H( NHCJ'LLNH I CO "Calculated for [H(NHC H,) NHl CSEXAMPLES VIII to X The following runs illustrate the reaction of thepetroleum sulfonic acid of Run 1 with the TEPA/urea adducts of Runs 2and 3. The usefulness of the products as motor fuel additives andlubricating oil additives is also demonstrated.

In Runs 8 the TEPA/urea adducts of Run 2 (30 gm) and 60 gm of SAE 10stock oil were heated to 145F in a 1-liter reactor. To the stirredmixture was added 715 ml of a solution containing 58.86 weight percentpetroleum sulfonic acid in SAE 10 stock oil, said addition requiring 45minutes with the temperature of the reaction mixture being maintained atl40150F. The ratio of equivalents of petroleum sulfonic acid per moleoriginal amine was 1.22. The product had a pH of 8.25 and was found tocontain 1.31 weight percent nitrogen and 1.2 weight percent sulfur.

Run 9 was conducted as described for Run 8 with the followingexceptions: 1200 ml of 58.86 percent petroleum sulfonic acid solution, a2-liter reactor, TEPA/urea adduct from Run 3 was used, addition time wasminutes, and after addition the temperature of the system was maintainedat 145F for 45 minutes. The ratio of equivalents of petroleum sulfonicacid per mole of original amine was 2.05. The product had a pH of 4.8and was found to contain 0.8 weight percent nitrogen.

Run 10 was conducted as described for Run 8 with the followingexceptions: 17 gm of TEPA/urea adduct from Run 3, 34 gm SAE 10 stock oiland 680 ml of 58.86 percent petroleum sulfonic acid solution were used;addition to acid to TEPA/urea adduct required 30 minutes. The ratio ofpetroleum sulfonic acid per mole of original amine was 2.05. Crudereaction mixture was combined with that from Run 9. The combined mixturewas found to have a pH of 4.8 and to contain 0.8 weight percentnitrogen.

The crude reaction mixture from Run 8 was evaluated as a motor fueladditive by a laboratory gasoline deposit test and also by a carburetordetergency test.

The laboratory gasoline deposit test utilized was a modification of themethod described in A Bench Technique for Evaluating the InductionSystem Deposit Tendencies of Motor Gasolines, A. A. Johnston and E.Dimitroff (Society of Automotive Engineers, Fuels and LubricantsMeeting, Houston, Texas, Nov. 1-3, 1966, Paper No. 660783).

The raw gasoline stock used in the gasoline deposit test was acommercial automotive premium gasoline sample containing tetraethyl leadand oxidation inhibitor but no other additives. The raw gasoline stockwas passed through a 0.3 micron filter after which 0.04 parts by weightsulfurized terpene per parts by weight filtrate was added. This producedthe gasoline source from which samples were taken for testing with andwithout the additives of this invention.

Briefly in accordance with the above-described modified procedure, thetest gasoline (2 ml/min) was mixed with a flow of air (28 ft /hr) toform a gasoline-air mixture. The mixture was discharged from a nozzle asa spray against an aluminum deposit pan of known weight. The deposit panwhich was preheated to 375F was maintained at that temperature while themixture was sprayed against it. After 250 ml of test gasoline wassprayed, the gasoline flow was terminated, but the airflow andtemperature were maintained constant for another 15 minutes. The airflowwas then terminated and the pan was allowed to cool to room temperature.Weighing of the pan then provided the weight of deposits in milligramsper 100 ml of test gasoline.

Evaluation results of the crude reaction mixture from Run 8 according tothe above-described spray test are recorded in Table I1.

TABLE 11 Fuel Deposit, mg

Without additive 1.5 With additive" 0.1

"Test gasoline contained 0.05 weight perccnt crudc reaction mixture fromRun 8.

The carburetor detergency test employed to evaluate the crude reactionmixture from Run 8 involved the use of test gasolines in a 170 cubicinch displacement 6 cylinder automobile engine with a removablecarburetor throat insert. Operation of the engine was for 23 continuoushours at 1,800 rpm and l 1.4 brake horsepower. Weighing the removableinsert after these conditions of operation gave the weight of depositsformed. The weight of deposits was determined both before and afterwashing the insert with n-heptane.

Evaluation results of the crude reaction mixture from Run 8 according tothe above-described carburetor detergency test are recorded in TableIII.

"Base gasoline stock containing 10 pounds per thousand barrels (P'TB) ofthe crude reaction product from Run 8.

The data in Tables 11 and III show the reduced deposit-formingtendencies of fuel containing this invention composition.

The evaluation of the invention composition obtained by combining thecrude reaction mixtures of Runs 9 and 10 as a dispersant for lubricatingoils was made using a laboratory carbon spot test and a standardautomotive Ford Sequence V B test (described in ASTM Special TechnicalPublication No. 3l5-C).

The laboratory carbon spot dispersancy test is conducted by stirring 50mg of carbon black into 10 gm of an oil blend containing 4 weightpercent of the candidate additive. A drop of the resulting slurry isthen dropped onto a polished Burns Block heated to a temperature of500F. The extent to which the carbon black is carried to the extremityof the resulting oil ring is a measure of the dispersancycharacteristics of the additive.

The combined crude reaction mixtures from Runs 9 and 10 received arating of excellent according to the above-described carbon spot test.

The results of the Sequence V B test conducted using the combined crudereaction mixtures from Runs 9 and 10 and compared to the SAErequirements (1973 SAE- Handbook Sec. J-183a, SAE Recommended Practicefor Engine Oil Performance, pp. 4l74l9) for a lubricating oil aretabulated in Table IV.

TABLE IV-Continued Lube Oil" SAE With Additive Requirements Oil RingPlugging, 7r 8 5' "A commercial SAE 10W-40 motor oil formulationcontaining calcium petroleum sulfonate, oxidation inhibitor, andviscosity index improver. This test formulation contained 10 weightpercent of the combined crude reaction mixture from Runs 9 and 10 inplace of the normally used commercial dispersant.

"Maximum values.

The data presented in Table IV show that the invention additive nearlyequalled or surpassed the SAE requirement in three of the five testcategories. Total varnish and oil ring plugging were below standard.

EXAMPLES XI TO XIII The following runs illustrate the reaction of thepetroleum sulfonic acid of Run 1 with the amine/thiourea adducts of Runs4, 5, and 6. The usefulness of the products as motor fuel additives andlubricating oil additives is also demonstrated.

In Run 11 the TEPA/thiourea adduct of Run 4 (60 gm) and 60 gm SAE 10stock oil were heated to 145F in a three-liter reactor. To the stirredmixture was added slowly (2% hours) 1756 ml of a 58.86 weight percentsolution of petroleum sulfonic acid from Run 1 in SAE 10 stock oil. Theratio of equivalents petroleum sulfonic acid per mole original amine was1.56. Following completion of the addition, the mixture was stirred anadditional one-half hour at 145F. Analysis showed that this reactionmixture contained 1.29 (avg. of three determinations) weight percent Nand 1.21 weight percent S.

Run 12 was run as described for Run 1 l with the following exceptions:gm TEPA/thiourea adduct from Run 5, 70 gm SAE 10 stock oil, and 2045 mlof petroleum sulfonic acid solution were used; and addition required 1/3 hours. The ratio of equivalents of petroleum sulfonic acid per moleof original amine was 1.56. The product had a pH of 6.98 and was foundto contain 0.94 (average of two determinations) weight percent N.

Run 13 was run in duplicate and the crude reaction mixtures werecombined. Run 13 was conducted as described for Run 11 with thefollowing exceptions: gm of TEPA/thiourea adduct from Run 6, 90 gm SAE10 stock oil, and 2634 ml of petroleum sulfonic acid solution were used;and addition required two hours. The ratio of equivalents of petroleumsulfonic acid per mole of original amine was 1.56. The combined productsexhibited a pH of 7.35 and were found to contain 1.16 (average of threedeterminations) weight percent N and 1.24 Weight percent S.

When subjected to the laboratory carbon spot dispersancy test describedin Examples VIII to X, the crude reaction mixtures of Runs 1 l and 12received an excellent rating; whereas that from Run 13 received anexcellent rating.

Sequence VB engine tests for evaluating the effectiveness of theinvention compositions were conducted as described in Examples VIII toX. The test additives were the crude reaction mixtures from Runs 11, 12,and 13. Results are tabulated in Table V with the comparative SAErequirements.

TABLE V Lube Oil with Additives SAE Run ll Run 12' Run 13" Req.

Total Sludge (50=clean) 44.3 39.3 37.6 42.5 Total Varnish (50=c|can)37.1 29.9 41.0 Piston Varnish (l=clean) 8.7 7.5 7.4 8.0 Oil RingPlugging, "/2 O 2 32 5 Oil Screen Plugging, 0 I2 24 5 "A commercial SAEtow-40 motor oil formulation containing calcium petroleum sulfonate.

"Test was Sequence VC (only slight modification of Sequence VB test).Formulation contained l0 weight percent of Run l3 additive.

The data in Table V indicate that Run 11 additive produced resultssurpassing the SAE requirements in four of the five test categories andslightly inferior in total varnish. The reasons for poor results withRuns 12 and l 3 additives are not well understood. Table I shows thatthe product of Run 5 contained 9.3 percent oxygen which is unexplained;no oxygen should have been present. Since the product of Run 5 was usedin Run 12, it could have resulted in the anomalous results in Table V.Table I also reveals that the sulfur content of the product from Run 6was lower than that from Run 4. This observation provides a possiblepartial explanation for the difference between the formulations usingRuns 1 l and 13 additives in Table V.

The crude reaction mixture from Run 1 l was evaluated according to thelaboratory gasoline deposit test described in Examples VIII to X. Theresults obtained using 0.05 weight percent of Run 1 l additive comparedto base gasoline stock containing no additive are given in Table VI.

TABLE VI Fuel Deposits (mg) Without additive l.5 With additive 0.1

TABLE VII Deposits (mg) Fuel Washed Without additive 17 With additive l1.8

The data in Tables VI and VII illustrate the depositreducingcharacteristics imparted to test gasolines by the compositions of thisinvention.

I claim:

1. A lubricating oil composition comprising a major proportion of alubricating oil containing a small but effective amount, sufficient toimpart increased detergency to said lubricating oil, of a dispersantadditive which is the reaction product obtained upon reacting a. apetroleum sulfonic acid with b. an adduct formed from 1. at least oneamine selected from primary monoamines having from 2 to 10, inclusive,carbon atoms, and polyamines represented by the formula H N[(CH ),NH],,Hwherein x is an integer of from 2 to 6 and y is an integer of from 1 to10, and

2. urea or thiourea.

2. A composition according to claim 1 wherein the lubricating oilcontains from about 0.2 to about 30 weight percent of said additive.

3. A composition according to claim 1 wherein said additive is thereaction product obtained upon reacting (a) a petroleum sulfonic acidprepared by sulfonating a petroleum hydrocarbon fraction having aviscosity within the range of 90 to 270 SUS at 2 10F and a viscosityindex of at least about 85 and (b) an adduct formed fromtetraethylenepentamine and urea.

4. A composition according to claim 1 wherein said additive is thereaction product obtained upon reacting (a) a petroleum sulfonic acidprepared by sulfonating a petroleum hydrocarbon fraction having aviscosity within the range of 90 to 270 SUS at 210F and a viscosityindex of at least about 85 and (b) an adduct formed fromtetraethylenepentamine and thiourea.

5. A motor fuel comprising a major proportion of motor fuel containing asmall but effective amount, sufficient to impart deposit-forming reducedtendencies to said motor fuel, of an additive which is the reactionproduct obtained upon reacting a. a petroleum sulfonic acid with b. anadduct formed from 1. at least one amine selected from primarymonoamines having from 2 to 10, inclusive, carbon atoms, and polyaminesrepresented by the formula H N[(CH ),NI-I],,I-I wherein x is an integerof from 2 to 6 and y is an integer of from I to 10, and

2. urea or thiourea.

6. A composition according to claim 5 wherein the motor fuel containsfrom about 0.001 to about 0.2 weight part of additive per 100 weightparts motor fuel.

7. A composition according to claim 5 wherein the motor fuel is adistillate boiling in the range of about to about 420F.

8. A composition according to claim 5 wherein said additive is thereaction product obtained upon reacting (a) a petroleum sulfonic acidprepared by sulfonating a petroleum hydrocarbon fraction having aviscosity within the range of 90 to 270 SUS at 210F and a viscosityindex of at least about and (b) an adduct formed fromtetraethylenepentamine and urea.

9. A composition according to claim 5 wherein said additive is thereaction product obtained upon reacting (a) a petroleum sulfonic acidprepared by sulfonating a petroleum hydrocarbon fraction having aviscosity within the range of to 270 SUS at 210F and a viscosity indexof at least about 85 and (b) an adduct formed fromtetraethylenepentamine and thiourea.

1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF ALUBRICATING OIL CONTAINING A SMALL BUT EFFECTIVE AMOUNT SUFFICIENT TOIMPART INCREASED DETERGENCY TO SAID LUBRICATING OIL OF A DISPERSANTADDITIVE WHICH IS THE REACTION PRODUCT OBTAINED UPON REACTING A APETROLEUM SULFONIC ACID WITH B. AN ADDUCT FORMED FROM
 1. AT LEAST ONEAMINE SELECTED FROM PRIMARY MONOAMINES HAVING FROM 2 TO 10 INCLUSIVECARBON ATOMS AND POLYAMINES REPRESENTED BY THE FORMULA H2N CH2)ZNH
 1. ATLEAST ONE AMINE SELECTED FROM PRIMARY MONOAMINES HAVING FROM 2 TO 10INCLUSIVE CARBON ATOMS AND POLYAMINES REPRESENTED BY THE FORMULAH2N(((CH2)XNH
 2. UREA OR THIOUREA.
 2. urea or thiourea.
 2. A compositionaccording to claim 1 wherein the lubricating oil contains from about 0.2to about 30 weight percent of said additive.
 2. UREA OR THIOUREA. 2.urea or thiourea.
 3. A composition according to claim 1 wherein saidadditive is the reaction product obtained upon reacting (a) a petroleumsulfonic acid prepared by sulfonating a petroleum hydrocarbon fractionhaving a viscosity within the range of 90 to 270 SUS at 210*F and aviscosity index of at least about 85 and (b) an adduct formed fromtetraethylenepentamine and urea.
 4. A composition according to claim 1wherein said additive is the reaction product obtained upon reacting (a)a petroleum sulfonic acid prepared by sulfonating a petroleumhydrocarbon fraction having a viscosity within the range of 90 to 270SUS at 210*F and a viscosity index of at least about 85 and (b) anadduct formed from tetraethylenepentamine and thiourea.
 5. A MOTOR FUELCOMPRISING A MAJOR PROPORTION OF MOTOR FUEL CONTAINING A SMALL BUTEFFECTIVE AMOUNT SUFFICIENT TO IMPART DEPOSIT-FORMING REDUCED TENDENCIESTO SAID MOTOR DUEL OF AN ADDITIVE WHICH IS THE REACTION PRODUCT OBTAINEDUPON REACTING A. A PETROLEUM SULFONIC ACID WITH B. AN ADDUCT FORMED FROM6. A composition according to claim 5 wherein the motor fuel containsfrom about 0.001 to about 0.2 weight part of additive per 100 weightparts motor fuel.
 7. A composition according to claim 5 wherein themotor fuel is a distillate boiling in the range of about 70* to about420*F.
 8. A composition according to claim 5 wherein said additive isthe reaction product obtained upon reacting (a) a petroleum sulfonicacid prepared by sulfonating a petroleum hydrocarbon fraction having aviscosity within the range of 90 to 270 SUS at 210*F and a viscosityindex of at least about 85 and (b) an adduct formed fromtetraethylenepentamine and urea.
 9. A composition according to claim 5wherein said additive is the reaction product obtained upon reacting (a)a petroleum sulfonic acid prepared by sulfonating a petroleumhydrocarbon fraction having a viscosity within the range of 90 to 270SUS at 210*F and a viscosity index of at least about 85 and (b) anadduct formed from tetraethylenepentamine and thiourea.